JP6422983B2 - Fishing hook - Google Patents

Description

The present invention relates to a surface-treated fishing hook and the like, and more particularly to a fishing hook and the like surface-treated with a metallic surfactant and the like.
Priority is claimed on Japanese Patent Application No. 2014-180793, filed September 5, 2014, the content of which is incorporated herein by reference.

Conventionally, the surface treatment of fishing hooks for fishing etc. is to improve the corrosion resistance by performing nickel plating or gold plating on the surface of the material of the hook, or coating the surface of the plating layer with acrylic resin or urethane resin. There was also one that
Furthermore, there is also a thing which formed the plating layer which combines the fluorine resin of a fine molecular structure with nickel- phosphorus alloy base material by electroless processing to the surface of a fishhook raw material (patent documents 1).
However, in the conventional surface treatment, the surface treatment can not be performed while maintaining the sharpness of the needle point, and it is not sufficient as the surface treatment of a fishing hook for fishing.
In addition, the conventional Teflon (registered trademark) plated coated fishing hook has low impact resistance, and when the fishing hook collides with a stone or the like, there is also a problem that the Teflon (registered trademark) plating is peeled off or chipped.

  On the other hand, as a method of processing a substrate surface to form a thin film, a metal-based surfactant having at least one or more hydrolysable groups, in an organic solvent, metal oxide or metal alkoxide partial hydrolysis product and water There is known a method of bringing a solution treated in step (1) into contact with the surface of a substrate (Patent Documents 2 and 3 and the like). In addition, as surface treatment agents for substrates, other fluorine-based surface treatment agents, thiols, sulfides, disulfides, etc. are also known, but all of these are applied to fishhooks or similar articles. Absent. Patent Document 3 exemplifies the use of a chemical adsorption film, but as an example of a needle, a needle for surgery, a sewing needle, a sewing needle, a folding needle, an injection needle, a surgical needle and a safety pin are exemplified. However, these are all completely different from those used in water for fishing and the like.

Japanese Patent Application Laid-Open No. 6-113699 WO 03/076064 pamphlet Japanese Patent Application Laid-Open No. 5-31356

  An object of the present invention is to provide a fishing hook for fishing etc. which is easy to bite to fish etc. and is excellent in durability.

MEANS TO SOLVE THE PROBLEM The present inventors of the present invention earnestly search results as a result of the above-mentioned subject, as a hook, metal type surfactant which has at least one or more hydroxyl groups or a hydrolysable group, a fluorine system surface treating agent, a thiol compound and a disulfide compound By treating the surface with a compound selected from the group consisting of the following, it is found that the stress at the time of biting and penetrating to fish etc. can be reduced, and the durability is further improved, and the present invention has been completed. .
That is, the present invention
(1) A fishing hook surface-treated with a compound selected from the group consisting of metal surfactants having at least one or more hydroxyl groups or hydrolysable groups, a fluorine-based surface treatment agent, a thiol compound and a disulfide compound,
(2) The metal-based surfactant having at least one or more hydroxyl group or hydrolyzable group is a compound represented by formula (I)
R ¹ _n MX _m-n (I)
(Wherein, R ¹ is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, a halogenated hydrocarbon group having 1 to 30 carbons which may have a substituent, a linking group Or a hydrocarbon group having 1 to 30 carbon atoms including C, or a halogenated hydrocarbon group having 1 to 30 carbon atoms including a linking group, and M represents a silicon atom, a germanium atom, a tin atom, a titanium atom, or a zirconium atom And at least one metal atom selected from the group consisting of: X represents a hydroxyl group or a hydrolysable group, and m represents a valence of M. n is any one of 1 to (m-1). R ¹ may be the same or different when n is 2 or more, and when (m−n) is 2 or more, X may be the same or different. And X, at least one of which is a hydroxyl group or a hydrolysable group) Fishhook according to which (1) is, and (3) hook is, in advance,
(A) Hydrolysis condensation product of epoxy group-containing trialkoxysilane,
(B) an alcohol having 1 to 5 carbon atoms, and / or an organic acid having a pKa at 25 ° C. in the range of 2.0 to 6.0, and
(C) The fishing hook according to (1) or (2), which is a fishing hook surface-treated with a thin film-forming composition containing polyamines.

  The fishhook formed with the organic thin film of the present invention can reduce stress at the time of biting and penetrating fish etc., so it is possible to enhance the fishing fruit and maintain its effect even after repeated use .

FIG. 6 is a view showing the piercing test result for the acupuncture needle obtained in Example 1.

(1) Compound for Surface Treatment of Fish Hook The fish hook according to the present invention is selected from the group consisting of metal surfactants having at least one or more hydroxyl groups or hydrolyzable groups, fluorine-based surface treatment agents, thiol compounds and disulfide compounds. Surface-treated with The surface treatment forms an organic thin film on the surface of the hook.
Below, each surface treatment compound is explained in full detail.

1) Metal-Based Surfactant Having at least One or More Hydroxyl Groups or Hydrolyzable Groups As the “metal-based surfactant having at least one or more hydroxyl groups or hydrolyzable groups” in the present invention, at least one or more hydroxyl groups or The hydrolyzable group is not particularly limited as long as it has a hydrolyzable functional group and a hydrophobic group in the same molecule, but a hydrolyzable group capable of reacting with active hydrogen on the surface of a hook to form a bond It is preferable to have. Incidentally, a hydroxyl group, in particular, a hydroxyl group directly bonded to a metal atom can react with active hydrogen to form a bond.
As the metal-based surfactant having at least one or more hydroxyl group or hydrolyzable group, specifically, a compound represented by formula (I)
R ¹ _n MX _m-n (I)
The compounds represented by can be preferably exemplified.

In the formula, R ¹ is a hydrocarbon group having 1 to 30, preferably 10 to 30, carbon atoms which may have a substituent, or 1 to 30 carbon atoms, preferably having a substituent. To 30 halogenated hydrocarbon groups, 1 to 30 carbon atoms including a linking group, preferably 10 to 30 hydrocarbon groups, or 1 to 30 carbon atoms including a linking group, preferably 10 to 30 halogenated hydrocarbons M represents a group, M represents at least one metal atom selected from the group consisting of silicon atoms, germanium atoms, tin atoms, titanium atoms, and zirconium atoms, and X represents a hydroxyl group or a hydrolysable group, m Represents the valence of M. n represents a positive integer of 1 to (m-1), and when n is 2 or more, R ¹ may be the same or different. When (m−n) is 2 or more, X may be the same or different, but at least one of X is a hydroxyl group or a hydrolysable group.

  The hydrocarbon group of the above-mentioned "hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (s)" is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-decyl Examples thereof include alkyl groups having 1 to 30 carbon atoms such as groups; alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl and propenyl groups; and aryl groups such as phenyl and naphthyl.

  As a halogenated hydrocarbon group of the above-mentioned "C1-C30 halogenated hydrocarbon group which may have a substituent", a C1-C30 halogenated alkyl group and a C1-C30 halogen are mentioned. And alkenyl aryl groups and halogenated aryl groups. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom etc. are mentioned, A fluorine atom is preferable. Specifically, groups in which one or more of hydrogen atoms in the hydrocarbon groups exemplified above are substituted with a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom can be mentioned.

  Among these, as the above-mentioned halogenated hydrocarbon group having 1 to 30 carbon atoms, a group in which two or more of hydrogen atoms in an alkyl group having 1 to 30 carbon atoms are substituted with a halogen atom is preferable. More preferred is a fluorinated alkyl group in which two or more of the hydrogen atoms in the alkyl group of 30 are substituted with a fluorine atom. When the fluorinated alkyl group has a branched structure, the branched portion is preferably a short chain having 1 to 4 carbon atoms, preferably 1 to 2 carbon atoms.

As the fluorinated alkyl group, a group in which one or more fluorine atoms are bonded to a terminal carbon atom is preferable, and a group having a CF ₃ group moiety in which _three fluorine atoms are bonded to a terminal carbon atom is more preferable. The terminal may be a hydrocarbon group which is not substituted by a fluorine atom, and may be a carbon chain in which a fluorine atom is substituted on the internal carbon chain. In the terminal part, it has a perfluoroalkyl moiety in which all hydrogen atoms of the alkyl group are substituted with a fluorine atom, and between the metal atom M described later and-(CH ₂ ) _h- (wherein h is 1) A group having an alkylene group represented by an integer of ̃6, preferably an integer of 2 to 4 is particularly preferable.

  The number of fluorine atoms in the fluorinated alkyl group is [(number of fluorine atoms in the fluorinated alkyl group) / (number of hydrogen atoms present in the alkyl group of the same carbon number corresponding to the fluorinated alkyl group) × 100]% When it represents, it is preferable that it is 60% or more, and it is more preferable that it is 80% or more.

  As a substituent of the above-mentioned "hydrocarbon group having 1 to 30 carbon atoms which may have a substituent" or "halogenated hydrocarbon group having 1 to 30 carbon atoms which may have a substituent", An amido group; an imide group; an alkoxycarbonyl group; an alkoxy group such as a methoxy group and an ethoxy group; a hydroxyl group and the like. It is preferable that the number of these substituents is 0-3.

  Specifically as the above-mentioned "hydrocarbon group having 1 to 30 carbon atoms containing a linking group", the above-mentioned "hydrocarbon group having 1 to 30 carbon atoms which may have a substituent" may be used. The same groups as those mentioned as the hydrocarbon group can be mentioned.

  Moreover, as the halogenated hydrocarbon group of the "C1-C30 halogenated hydrocarbon group containing a linking group", specifically, the above-mentioned "C1-C30 carbon group which may have a substituent group" The same groups as those described as the halogenated hydrocarbon group for the “halogenated hydrocarbon group” can be mentioned.

  The linking group is preferably present between carbon-carbon bonds of a hydrocarbon group or a halogenated hydrocarbon group, or between carbon of a hydrocarbon group and a metal atom M described later.

Specific examples of the linking group include -O-, -S-, -SO _2- , -CO-, -C (= O) O- or -C (= O) NR ^51- (wherein, R ⁵¹ represents And hydrogen atoms; and alkyl groups such as methyl, ethyl, n-propyl and isopropyl.

Among them, R ¹ is an alkyl group having 1 to 30 carbon atoms, a fluorinated alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group containing a linking group from the viewpoint of water repellency and durability. Is preferred.

More preferable specific examples of R ¹ include CH _3- , CH ₃ CH _2- , (CH ₃ ) ₂ CH-, (CH ₃ ) ₃ C-, CH ₃ (CH ₂ ) _2- , and CH ₃ (CH _{2). ) 3 -, CH 3 (CH} 2) 4 -, CH 3 (CH 2) 5 -, CH 3 (CH 2) 6 -, CH 3 (CH 2) 7 -, CH 3 (CH 2) 8 -, CH _{3 (CH 2) 9 -,} CH 3 (CH 2) 10 -, CH 3 (CH 2) 11 -, CH 3 (CH 2) 12 -, CH 3 (CH 2) 13 -, CH 3 (CH 2) _14- , CH ₃ (CH ₂ ) _15- , CH ₃ (CH ₂ ) _16- , CH ₃ (CH ₂ ) _17- , CH ₃ (CH ₂ ) _18- , CH ₃ (CH ₂ ) _19- , CH _{3 (CH 2) 20 -, CH} 3 (CH 2) 21 -, CH 3 (CH _{) 22 -, CH 3 (CH} 2) 23 -, CH 3 (CH 2) 24 -, CH 3 (CH 2) 25 -, CF 3 -, CF 3 CF 2 -, (CF 3) 2 CF -, ( _{CF 3) 3 C-, CF 3} (CH 2) 2 -, CF 3 (CF 2) 3 (CH 2) 2 -, CF 3 (CF 2) 5 (CH 2) 2 -, CF 3 (CF 2) ₇ (CH ₂ ) _2- , CF ₃ (CF ₂ ) ₃ (CH ₂ ) _3- , CF ₃ (CF ₂ ) ₅ (CH ₂ ) _3- , CF ₃ (CF ₂ ) ₇ (CH ₂ ) _3- , _{CF 3 (CF 2) 9 (} CH 2) 2 -, CF 3 (CF 2) 6 (CH 2) 2 -, CF 3 (CF 2) 4 O (CF 2) 2 (CH 2) 2 -, CF 3 (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) _3- , CF ₃ (CF ₂ ) ₇ O (CF ₂ ) ₂ (CH ₂ ) _2- , CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) _2- , CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) _3- , CF ₃ (CF ₂ ) ₃ O [CF _{(CF 3) CF (CF 3} ) O] 2 CF (CF 3) CONH (CH 2) 3 -, CH 3 (CF 2) 7 (CH 2) 2 -, CH 3 (CF 2) 8 (CH 2) _{2 -, CH 3 (CF 2} ) 9 (CH 2) 2 -, CH 3 (CF 2) 10 (CH 2) 2 -, CH 3 (CF 2) 11 (CH 2) 2 -, CH 3 (CF 2 ) ₁₂ (CH ₂ ) _2- , CH ₃ (CF ₂ ) ₇ (CH ₂ ) _3- , CH ₃ (CF ₂ ) ₉ (CH ₂ ) _3- , CH ₃ (CF ₂ ) ₁₁ (CH ₂ ) _{3- , CH 3 CH 2 (CF 2} ) 6 (CH 2) 2 -, CH 3 CH 2 (CF ₂ ) ₈ (CH ₂ ) _2- , CH ₃ CH ₂ (CF ₂ ) ₁₀ (CH ₂ ) _2- , CH ₃ (CF ₂ ) ₄ O (CF ₂ ) ₂ (CH ₂ ) _2- , CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ O (CH ₂ ) _3- , CH ₃ (CF ₂ ) ₈ (CH ₂ ) ₂ O (CH ₂ ) _3- , CH ₃ (CF ₂ ) ₉ (CH ₂ ) _{2 O (CH 2) 3 -,} CH 3 CH 2 (CF 2) 6 (CH 2) 2 O (CH 2) 3 -, CH 3 (CF 2) 6 CONH (CH 2) 3 -, CH 3 (CF 2 _{) 8 CONH (CH 2) 3} -, CH 3 (CF 2) 3 O [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 -, but and the like Not limited to these.

  M represents one type of atom selected from the group consisting of silicon atoms, germanium atoms, tin atoms, titanium atoms, and zirconium atoms. Among these, silicon atoms are particularly preferable in view of availability of raw materials, reactivity, and the like.

  X represents a hydroxyl group or a hydrolyzable group, and the hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes. Specifically, an alkoxy group having 1 to 6 carbon atoms which may have a substituent; a hydrocarbon oxy group which may have a substituent (with the exception of the alkoxy group); having a substituent Examples thereof include acyloxy groups which may be present; halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; isocyanate groups; cyano groups; amino groups;

  As the "C1-C6 alkoxy group", methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n -A hexyloxy group etc. are mentioned.

Examples of the "hydrocarbon oxy group" other than the alkoxy group include alicyclic hydrocarbon oxy groups such as cyclopropyl oxy group, cyclopropyl methyl oxy and cyclohexyloxy group; and alkenyl oxy oxy groups such as vinyl oxy group, allyloxy group and norbornyloxy group Group; alkynyloxy group such as propargyloxy group; aryloxy group such as phenoxy group, naphthyloxy group etc .; arylalkyloxy group such as benzyloxy group, phenethyloxy group etc. As the acyloxy group, alkyl such as acetoxy group, propionyloxy group Examples thereof include a carbonyloxy group; an alkenyl carbonyloxy group such as a (meth) acryloyloxy group; and an aryl carbonyloxy group such as a benzoyloxy group.

Examples of the substituent “which may have a substituent” in X include a carboxyl group, an amido group, an imide group, an alkoxycarbonyl group, a hydroxyl group and the like.
Especially as X, a hydroxyl group, a halogen atom, a C1-C6 alkoxy group, an acyloxy group, or an isocyanate group is preferable, and a C1-C4 alkoxy group or an acyloxy group is more preferable.

m represents the valence of the metal atom M.
n represents any positive integer from 1 to (m-1). In order to produce a high density organic thin film, n is preferably 1. When n is 2 or more, R ¹ may be the same or different. When (m−n) is 2 or more, X may be the same or different, but at least one of X is a hydroxyl group or a hydrolysable group.

Among the compounds represented by the formula (I), one of the preferred embodiments is a compound of the formula (II)
The compound represented by these can be illustrated.
In the formulae, M, X and m have the same meanings as described above. R ^{21 to} R ²³ , R ³¹ and R ³² each independently represent a hydrogen atom or a fluorine atom, and R ⁴ represents an alkylene group, a vinylene group, an ethynylene group, an arylene group, or a silicon atom and / or an oxygen atom It represents a divalent linking group. Y represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group. p represents 0 or a natural number, and q represents 0 or 1. When p is 2 or more, the groups represented by the formula: C (R ³¹ ) (R ³² ) may be the same or different. r represents 0 or a positive integer from 1 to (m-2), and when r is 2 or more, Y may be the same or different, and when (m-r-1) is 2 or more And X may be the same or different. However, at least one of Y and X is a hydroxyl group or a hydrolysable group.

Specifically as R ⁴ in formula (II), functional groups shown in the following formula can be exemplified.

In the above formulae, a and b represent one or more arbitrary natural numbers.
Y represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group or a t-pentyl group Alkyl groups such as n-hexyl group and isohexyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy Group, an alkoxy group such as n-hexyloxy group; a fluorine-containing alkyl group wherein some or all hydrogen atoms of the alkyl group are substituted by a fluorine atom; or some or all hydrogen atoms of an alkoxy group are substituted by a fluorine atom It represents a substituted fluorine-containing alkoxy group or the like.

  r represents 0 or a positive integer of 1 to (m-2), but r is preferably 0 in order to produce a high density adsorptive film. When r is 2 or more, Y may be the same or different. When (m-r-1) is 2 or more, X may be the same or different. However, at least one of Y and X is a hydroxyl group or a hydrolysable group.

  Specific examples of the compound represented by the formula (I) include those shown below. In addition, although the compound whose metal atom M is a silicon atom is shown as a representative example in the following, this invention is not limited to these. Further, the hydrolyzable group is not limited to the exemplified functional group, and may be one having another hydrolyzable group bonded thereto.

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) ₃
CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OCH 3) 3
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OCH 3) 3
CH ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) 3
_{CF 3 (CF 2) 7 (} CH = CH) 3 Si (OCH 3) 3
_{CH 3 CH 2 O (CH 2} ) 15 Si (OC 2 H 5) 3
_{CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 3
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
_{CF 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 3
CH ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
CF ₃ COO (CH ₂ ) ₁₅ Si (OC ₂ H ₅ ) ₃
CF ₃ COO (CH ₂ ) ₁₅ Si (OCH ₃ ) _{3
CF 3 (CF 2) 9 (} CH 2) 2 Si (OC 2 H 5) 3
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OC ₂ H ₅ ) _{3
CF 3 (CF 2) 7 (} CH = CH) 3 Si (OC 2 H 5) 3
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) 3
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OC 2 H 5) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) 2 (OC 2 H 5)
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) 2 (OCH 3)

CF ₃ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
CF 3 (CF 2) 3 (} CH 2) 2 Si (OCH 3) 3
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) 3
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OCH ₃ ) _{3
CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) 3
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 3 Si (OCH 3) 3
_{CF 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OCH ₃ ) _{3
CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) -
CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃

_{CF 3 (CF 2) 3 (} CH 2) 2 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (CH 3) (OCH 3) 2
_{CF 3 (CH 2) 2 Si} (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 3 (} CH 2) 3 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 5 (} CH 2) 3 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 7 (} CH 2) 3 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 2 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 3 Si (CH 3) (OCH 3) 2
_{CF 3 (CF 2) 4 (} CH 2) 2 O (CH 2) 3 Si (CH 3) (OCH 3) 2
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) (OCH ₃ ) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) _{2
CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) -
CONH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂
CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) _{3
CH 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) 2
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (NCO) _{3
CH 3 (CF 2) 8 (} CH 2) 2 Si (OCH 3) 3
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (NCO) 3
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (NCO) _{3
CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OCH 3) 3
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (NCO) 3
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (OCH 3) 3
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (NCO) 3
_{CH 3 CH 2 (CF 2)} 10 (CH 2) 2 Si (OCH 3) 3
_{CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) 3
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OCH 3) 3
CH ₃ (CF ₂ ) ₆ CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃
CH ₃ (CF ₂ ) ₈ CONH (CH ₂ ) ₃ Si (OCH ₃ ) _{3
CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) -
CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₃

_{CH 3 CH 2 O (CH 2} ) 15 Si (OCH 3) (OH) 2
_{CF 3 CH 2 O (CH 2} ) 15 Si (OCH 3) (OH) 2
_{CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OCH 3) (OH) 2
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OCH 3) (OH) 2
_{CH 3 COO (CH 2) 15} Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH = CH) 3 Si (OCH 3) (OH) 2
_{CH 3 CH 2 O (CH 2} ) 15 Si (OC 2 H 5) (OH) 2
_{CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) (OH) 2
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) (OH) 2
_{CF 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) (OH) 2
_{CH 3 COO (CH 2) 15} Si (OC 2 H 5) (OH) 2
_{CF 3 COO (CH 2) 15} Si (OC 2 H 5) (OH) 2
_{CF 3 COO (CH 2) 15} Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 9 (} CH 2) 2 Si (OC 2 H 5) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (OC 2 H 5) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OC 2 H 5) (OH) 2
_{CF 3 (CF 2) 7 (} CH = CH) 3 Si (OC 2 H 5) (OH) 2
_{CF 3 (CF 2) 9 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 9 (} CH 2) 2 Si (CH 3) (OH) 2

_{CH 3 CH 2 O (CH 2} ) 15 Si (OCH 3) 2 (OH)
_{CF 3 CH 2 O (CH 2} ) 15 Si (OCH 3) 2 (OH)
_{CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OCH 3) 2 (OH)
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OCH 3) 2 (OH)
_{CH 3 COO (CH 2) 15} Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 CH 2 O (CH 2} ) 15 Si (OC 2 H 5) 2 (OH)
_{CF 3 (CF 2) 7 (} CH = CH) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OC 2 H 5) 2 (OH)
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 2 (OH)
_{CF 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OC 2 H 5) 2 (OH)
_{CH 3 COO (CH 2) 15} Si (OC 2 H 5) 2 (OH)
_{CF 3 COO (CH 2) 15} Si (OC 2 H 5) 2 (OH)
_{CF 3 COO (CH 2) 15} Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 9 (} CH 2) 2 Si (OC 2 H 5) 2 (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (OC 2 H 5) 2 (OH)
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OC 2 H 5) 2 (OH)

_{CF 3 (CF 2) 7 (} CH = CH) 3 Si (OC 2 H 5) 2 (OH)
_{CF 3 (CF 2) 9 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OC 2 H 5) (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)

_{CF 3 (CH 2) 2 Si} (OCH 3) (OH) 2
_{CF 3 (CF 2) 3 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 3 (} CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 3 Si (OCH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OCH ₃ ) (OH) _{2
CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) (OH) 2

_{CF 3 (CH 2) 2 Si} (OCH 3) 2 (OH)
_{CF 3 (CF 2) 3 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 3 (} CH 2) 3 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 5 (} CH 2) 3 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 7 (} CH 2) 3 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 3 Si (OCH 3) 2 (OH)
_{CF 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (OCH ₃ ) ₂ (OH)
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OCH ₃ ) ₂ (OH)
_{CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) 2 (OH)

_{CH 3 (CH 2) 7 Si} (OCH 3) (OH) 2
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (NCO) (OH) 2
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (NCO) (OH) 2
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (NCO) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (NCO) (OH) 2
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (NCO) (OH) 2
_{CH 3 CH 2 (CF 2)} 10 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 6 CONH} (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 8 CONH} (CH 2) 3 Si (OCH 3) (OH) 2
_{CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) (OH) 2

_{CF 3 (CF 2) 3 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CH 2) 2 Si} (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 3 (} CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 5 (} CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 7 (} CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 4 (} CH 2) 2 O (CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 7 CONH} (CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 7 CONH} (CH 2) 3 Si (CH 3) (OCH 3) (OH)
_{CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (CH 3) (OCH 3) (OH)
CH ₃ (CH ₂ ) ₇ Si (OCH ₃ ) ₂ (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OCH 3) (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 9 (} CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (NCO) 2 (OH)
_{CH 3 CH 2 (CF 2)} 10 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 6 CONH} (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 8 CONH} (CH 2) 3 Si (OCH 3) 2 (OH)
_{CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OCH 3) 2 (OH)

CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) _{3
CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OH) 3
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OH) 3
CH ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH = CH) ₃ Si (OH) ₃
CH ₃ CH ₂ O (CH ₂ ) ₁₅ Si (OH) _{3
CH 3 (CH 2) 2 Si} (CH 3) 2 (CH 2) 15 Si (OH) 3
_{CH 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OH) 3
_{CF 3 (CH 2) 6 Si} (CH 3) 2 (CH 2) 9 Si (OH) 3
CH ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ COO (CH ₂ ) ₁₅ Si (OH) ₃
CF ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH = CH) ₃ Si (OH) _{3
CF 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) 2 (OH)
CF ₃ (CH ₂ ) ₂ Si (OH) _{3
CF 3 (CF 2) 3 (} CH 2) 2 Si (OH) 3
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₂ Si (OH) ₃
CF ₃ (CF ₂ ) ₃ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₅ (CH ₂ ) ₃ Si (OH) ₃
CF ₃ (CF ₂ ) ₇ (CH ₂ ) ₃ Si (OH) _{3
CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OH) 3
_{CF 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 3 Si (OH) 3
_{CF 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CF 3 (CF 2) 7 CONH} (CH 2) 2 Si (OH) 3
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (OH) _{3
CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OH) 3
CH ₃ (CH ₂ ) ₇ Si (OH) _{3
CH 3 (CF 2) 7 (} CH 2) 2 Si (OH) 3
_{CH 3 (CF 2) 8 (} CH 2) 2 Si (OH) 3
CH ₃ (CF ₂ ) ₉ (CH ₂ ) ₂ Si (OH) _{3
CH 3 CH 2 (CF 2)} 6 (CH 2) 2 Si (OH) 3
_{CH 3 CH 2 (CF 2)} 8 (CH 2) 2 Si (OH) 3
_{CH 3 CH 2 (CF 2)} 10 (CH 2) 2 Si (OH) 3
_{CH 3 (CF 2) 4 O} (CF 2) 2 (CH 2) 2 Si (OH) 3
_{CH 3 (CF 2) 7 (} CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CH 3 (CF 2) 8 (} CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CH 3 (CF 2) 9 (} CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CH 3 CH 2 (CF 2)} 6 (CH 2) 2 O (CH 2) 3 Si (OH) 3
_{CH 3 (CF 2) 6 CONH} (CH 2) 3 Si (OH) 3
_{CH 3 (CF 2) 8 CONH} (CH 2) 3 Si (OH) 3
_{CH 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (OH) 3
_{CF 3 (CF 2) 3 (} CH 2) 2 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 2 Si (CH 3) (OH) 2
_{CF 3 (CH 2) 2 Si} (CH 3) (OH) 2
_{CF 3 (CF 2) 3 (} CH 2) 3 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 5 (} CH 2) 3 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 7 (} CH 2) 3 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 2 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 4 (} CF 2) 2 (CH 2) 3 Si (CH 3) (OH) 2
_{CF 3 (CF 2) 4 (} CH 2) 2 O (CH 2) 3 Si (CH 3) (OH) 2
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₂ Si (CH ₃ ) (OH) ₂
CF ₃ (CF ₂ ) ₇ CONH (CH ₂ ) ₃ Si (CH ₃ ) (OH) _{2
CF 3 (CF 2) 3 O} [CF (CF 3) CF (CF 3) O] 2 CF (CF 3) CONH (CH 2) 3 Si (CH 3) (OH) 2
_{CH 3 (CF 2) 7 (} CH 2) 2 Si (CH 3) (OH) 2

  These compounds can be used alone or in combination of two or more.

2) Fluorine-Based Surface Treatment Agent The fluorine-based surface treatment agent according to the present invention contains, in addition to the above-mentioned silicon compound, fluoroalkyl and poly (fluoroalkyleneoxy), and the terminal contains a silicon compound, carboxylic acid, sulfonic acid, alcohol etc. Monomers and polymer compounds.
As specific products of the fluorine-based surface treatment agent, OPTOOL (registered trademark, Daikin Industries), Durasurf (registered trademark, Harvest), Nobek EGC-1720 (registered trademark, Sumitomo 3M), Florosurf (registered trademark, Fluorotechnology) Asahi Guard (registered trademark, Asahi Glass), SF Coat (registered trademark, AGC Seimi Chemical), and the like.
These fluorine-based surface treatment agents can be used alone or in combination of two or more.

3) Thiol Compound or Disulfide Compound The thiol compound or disulfide compound in the present invention is not particularly limited as long as it can be used for surface treatment of a fishing hook, and examples thereof include the following compounds.

Thiol compounds alkanethiols such as methanethiol, ethanethiol, propanethiol, octadecyl mercaptan;
Benzenethiol, chlorobenzenethiol, bromobenzenethiol, fluorobenzenethiol, pentafluorobenzenethiol, pentachlorobenzenethiol, nitrothiophenol, 2-mercapto-5-nitrobenzimidazole, perfluorodecanethiol, pentafluorothiophenol, 4-trichoro Aromatic thiols such as fluoromethyl-2,3,5,6-tetrafluorothiophenol, 5-chloro-2-mercaptobenzimidazole, methoxybenzenethiol, naphthalenethiol, toluenethiol, aminothiophenol, methoxybenzenethiol;
The following general formula such as triazine trithiol, triazine trithiol monosodium, triazine trithiol disodium, triazine trithiol di (diethanolamine), anilino triazine dithiol, dibutylamino triazine dithiol, etc.

(Wherein, R _a is —SH, —OH, NHR ₂ , NHR ₃ or SR ₂ ; R ₂ and R ₃ are the same or different alkyl group having 1 to 8 carbon atoms, phenyl group, or benzyl group, M Is a triazine thiol compound represented by -H, -Na, -K or an amine group;

Pentaerythritol tetrakis (6-mercapto-5-hydroxy-2-methyl-3-oxahexyl) ether, pentaerythritol tetrakis (9-mercapto-8-hydroxy-2,5-dimethyl-3,6-dioxanonyl) ether, penta Erythritol tetrakis (12-mercapto-11-hydroxy-2,5,8-trimethyl-3,6,9-trioxadodecyl) ether, pentaerythritol tris (6-mercapto-5-hydroxy-2-methyl-3-oxa) Hexyl) ether, pentaerythritol tris (9-mercapto-8-hydroxy-2,5-dimethyl-3,6-dioxanonyl) ether, pentaerythritol tris (12-mercapto-11-hydroxy-2,5,8-trimethyl- 3,6,9-Trioxadodecyl) ether, trimethylolpropane Squirrel (6-mercapto-5-hydroxy-2-methyl-3-oxahexyl) ether, trimethylolpropane tris (9-mercapto-8-hydroxy-2,5-dimethyl-3,6-dioxanonyl) ether, trimethylol Propane tris (12-mercapto-11-hydroxy-2,5,8-trimethyl-3,6,9-trioxadodecyl) ether, pentaerythritol tetrakis (6-mercapto-4-thiahexyl) ether, pentaerythritol tris (6 -Mercapto-4-thiahexyl) ether, trimethylolpropane tris (6-mercapto-4-thiahexyl) ether, pentaerythritol tetrakis mercaptoacetate, pentaerythritol tetrakis mercaptopropionate, trimethylolpropane trismercaptoacetate Trimethylolpropane trismercaptopropionate, tris (6-mercapto-4-thiahexyl) isocyanurate, 1,2-dimercaptoethylthio-3-mercaptopropane, 1,2-bis-2- (mercaptoethylthio)- The following general formula R (SH) _n such as 3-mercaptopropane and 1,2,3-trimercaptopropane
(In the formula, R is a hydrocarbon group other than a heterocyclic ring which may contain an ether bond, a sulfide bond and an organic functional group, and n is an integer of 3 or more).

Disulfide compound The following general formula R ^a -S-S-R ^b such as diphenyl disulfide, tolyl disulfide, dibutyl disulfide, dioctadecyl disulfide, etc.
(Wherein, R ^a and R ^{b each} represent an alkyl group having 2 to 18 carbon atoms or an aryl group, and R ^a and R ^b may be the same or different). Be The disulfide compound obtained by oxidizing the said thiol compound can also be illustrated concretely.

(2) Composition for surface treatment of fishing hook As a composition for treating the surface of a fishing hook, each of the above-mentioned compounds for surface treatment is a hydrocarbon solvent, a fluorocarbon solvent, a silicone solvent, etc. It is preferable to use by diluting with an organic solvent, and among them, hydrocarbon solvents are more preferable, and those having a boiling point of 100 to 250 ° C. are particularly preferable.

Further, as such organic solvents, specifically, n-hexane, cyclohexane, benzene, toluene, xylene, petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, kerosene, ligroin hydrocarbon solvents _{like; CBr 2 ClCF 3, CClF 2} CF 2 CCl 3, CClF 2 CF 2 CHFCl, CF 3 CF 2 CHCl 2, CF 3 CBrFCBrF 2, CClF 2 CClFCF 2 CCl 3, Cl (CF 2 CFCl) ₂ Fluorocarbon solvents such as chlorofluorocarbon solvents such as ₂ Cl, Cl (CF ₂ CFCl) ₂ CF ₂ CCl ₃ , Cl (CF ₂ CFCl) ₃ Cl, fluorocarbon solvents such as Fluorinert (manufactured by 3M), and Afred (manufactured by Asahi Glass); Dimethyl silicone, phenyl Silicone solvents such as silicone, alkyl modified silicone, polyether silicone and the like; These solvents may be used alone or in combination of two or more.

The content of the compound for surface treatment of hooks in the composition is not particularly limited, but is preferably in the range of 0.1 to 30% by weight based on the whole composition from the viewpoint of producing a denser organic thin film. .
In addition, when the compound for surface treatment is the metal-based surfactant, it is preferable to use other components after addition, and it is preferable to use WO2003 / 076064, WO2004 / 01810, WO2006 / 009202, WO2008. It can be prepared according to the method described in Japanese Patent Application Publication No. / 059840 or WO 2009/104424. As a composition for surface treatment containing a metallic surfactant, SAMLAY (a registered trademark, n-octadecyl trimethoxysilane containing, Nippon Soda Co., Ltd. make) etc. are mentioned, for example.

(3) Surface treatment method of fishing hook The method of surface-treating a fishing hook with the above-mentioned composition is explained below.
In the present invention, a fishing hook or the like for fishing generally has a shaft portion having a base end to which a fishing line is attached, and a folded portion curved and extended from the tip of the shaft portion. The shape is not particularly limited as long as it can be used for fishing or the like.
The material of the hook is carbon steel, stainless steel or the like, and may be plated with a metal such as nickel, tin, brass or gold.

In the case of a fishing hook made of a material having no hydroxyl group on the surface, the surface of the fishing hook can be previously treated in a plasma atmosphere containing oxygen, or can be corona-treated to introduce a hydrophilic group. The hydrophilic group, a hydroxyl group (-OH) is preferred, -COOH having an active hydrogen, -CHO, = NH, or the like functional group such as -NH _2.
If the shape is complicated and the above operation can not be carried out sufficiently, by washing the hook with an alkaline aqueous solution with an alkaline substance concentration of 1 to 20% by mass for 1 to 60 minutes, the lipid attached to the hook surface is decomposed The hook surface can be activated.

The alkaline aqueous solution to be used is not particularly limited as long as it is an aqueous solution exhibiting alkalinity.
For example, an aqueous solution containing an inorganic salt such as an alkali metal as an alkaline substance can be mentioned. As the inorganic salt, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium phosphate, sodium silicate, sodium borate and the like can be mentioned. If necessary, surfactants, water-soluble organic solvents such as alcohols and ketones, ozone water, and hydrogen peroxide water may be mixed and used within the scope of the object of the present invention.

  The concentration of the alkaline substance in the alkaline aqueous solution is preferably in the range of 1 to 20% by mass, and more preferably in the range of 1 to 10% by mass.

  The method of washing a fishing hook with an alkaline aqueous solution is not particularly limited as long as the fishing hook is brought into contact with the alkaline aqueous solution. For example, the fishing hook may be hung by spraying an alkaline aqueous solution, or the fishing hook is immersed in the alkaline aqueous solution. May be The time for which the hook and the alkaline aqueous solution are brought into contact with each other is not particularly limited, but is preferably 1 to 60 minutes, from the viewpoint of the balance between the washing efficiency of the hook and the washing effect and corrosion resistance. It is more preferable that it is a range. Moreover, it is preferable to carry out an ultrasonic treatment in the state which immersed the fishhook in alkaline aqueous solution from the more outstanding cleaning effect being acquired. The conditions of the ultrasonic treatment are not particularly limited, but treatment at a frequency of 25 to 30 KHz, a treatment time of 1 to 20 minutes, and a temperature of 20 to 50 ° C. is preferably mentioned.

  In the present invention, it is preferable that the step of washing the fishing hook with distilled water and / or the step of washing with an organic solvent be further added before and / or after the step of washing with an alkaline aqueous solution. As a result, it is possible to remove impurities such as dust, dirt and organic matter on the surface of the hook more highly, and to form the organic thin film more densely and strongly. In the case of having both the step of washing with distilled water and the step of washing with an organic solvent, the order of the step of washing with distilled water and the step of washing with an organic solvent does not matter. It is preferable to have the step of When the step of washing with distilled water and / or the step of washing with an organic solvent is performed after the step of washing with an alkaline aqueous solution, the step of washing with distilled water and / or the step of washing with an organic solvent Although it may have after the process to wash with, it is preferable to have before the process to wash with the organic solvent mentioned later.

  Here, distilled water used in the washing step is not particularly limited, but from the viewpoint of obtaining a better washing effect, distilled water having a resistance value of 10 mega ohms or more is preferable, and a distillation value of 15 mega ohms or more is preferable More preferably, it is water.

  Also, the organic solvent used in the washing step is not particularly limited, but alcohols such as ethanol and isopropanol are preferable, and ethanol and isopropanol are particularly preferable.

  Further, the washing method in the step of washing with distilled water and the step of washing with an organic solvent is not particularly limited. For example, distilled water or an organic solvent may be sprayed or showered on a hook or the like The fishing hook may be immersed in distilled water or an organic solvent. It is preferable to perform ultrasonic treatment in a state in which the fishing hook is immersed in distilled water or an organic solvent, because a better cleaning effect is obtained. As the specific conditions of the ultrasonic treatment, the same conditions as those in the case where the fishing hook is immersed in ozone water or hydrogen peroxide water and ultrasonicated can be exemplified. In addition, if a physical method of exposing to ultraviolet light, ozone, and plasma is further used in combination, a further excellent cleaning effect can be obtained.

  The method for contacting the surface treatment composition to the hook surface is not particularly limited, and any known method can be used. Specifically, dip method, spin coat method, spray method, roller coat method, Mayer bar method, screen printing method, brush coating method etc. may be mentioned, and among these, dip method is preferable.

  The temperature at which the surface treatment composition is in contact with the hook surface is not particularly limited as long as the solution of the present invention can maintain stability. Usually, the reaction can be carried out in the range from room temperature to the reflux temperature of the solvent used for preparation of the solution. In order to bring the temperature suitable for contact, the surface treatment composition may be heated or the hook itself may be heated.

  Ultrasound can also be used to promote film formation. The step of contacting the surface of the hook may be performed at one time for a long time or may be applied for a short time divided into several times.

  After the surface treatment composition is brought into contact with the hook surface, a washing step may be provided to remove excess reagent, impurities and the like attached to the membrane surface. The film thickness can be further controlled by providing the cleaning step. The organic solvent in the step of washing with an organic solvent is not particularly limited, but hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, benzene, toluene and xylene are preferable. The cleaning method is not particularly limited as long as it can remove surface deposits. Specifically, a method of immersing a fishing hook in a solvent capable of dissolving the used composition for surface treatment; a method of leaving in the air under vacuum or normal pressure to evaporate; inert gas such as dry nitrogen gas Method to spray and blow off; Moreover, since a more excellent cleaning effect is obtained, it is mentioned as a more preferable method that ultrasonic treatment is performed in the state where the fishing hook is immersed in the above-mentioned organic solvent.

  It is preferable to further have a step of drying the hook that has been washed with the organic solvent after the step of washing with the organic solvent. The drying method is not particularly limited, and the solution on the surface of the hook may be made by an air knife or the like, or it may be naturally dried, or a method of applying warm air may be exemplified. By applying heat to the organic thin film, the organic thin film is stabilized more, so a method of applying warm air is preferable.

  In addition, since the organic thin film is more stabilized than the case where heat is not applied to the hook when drying the hook, it is preferable to further include the step of applying heat to the hook. Although the temperature to heat can be suitably selected by the material of a fishing hook, and stability of an organic thin film, the range of 40-70 degreeC can be mentioned preferably, for example.

(4) Surface treatment carried out before the treatment with the above-mentioned composition for surface treatment In the case of a fishing hook made of a material having no active hydrogen on the surface, SiCl ₄ , SiHCl ₃ , SiH ₂ Cl ₂ , Cl −. (SiCl ₂ O) _c -SiCl ₃ (wherein, c represents 0 or a natural number). After contacting at least one compound selected from the above, silica having active hydrogen on the surface by dehydrochlorination reaction. An underlayer can also be formed.
In addition, for hooks coated with clear coat, color coat, etc., (a) hydrolysis condensation product of epoxy group-containing trialkoxysilane, (b) alcohol having 1 to 5 carbon atoms, and / or at 25 ° C. It is preferable to surface-treat the composition for thin film formation containing the organic acid of pKa in the range of 2.0-6.0, and (c) polyamines. Hereinafter, the composition for forming a thin film used in the present invention will be described.

1) Hydrolysis condensation product of epoxy group-containing trialkoxysilane The hydrolysis condensation product of epoxy group-containing trialkoxysilane shown in the above (a) is a condensed polymer or oligomer of epoxy group-containing trialkoxysilane.
The epoxy group-containing trialkoxysilane as a raw material used for producing the epoxy group-containing trialkoxysilane hydrolysis condensate used in the method of the present invention and / or the hydrolysis condensate thereof is a functional group converted by hydrolysis etc. The structure is not particularly limited as long as it is a trialkoxysilane containing an epoxy group in addition to the moiety, but for example, it is possible to exemplify a compound represented by the following formula (I-1) or (I-2) Can.

R ^s -Si (OR ^t ) ₃ ... (I-1)
R ^s -Si (OR ^t ) ₂ -O-Si (OR ^t ) ₂ R ^s (I-2)

In the formula, R ^s represents a hydrocarbon group which has an epoxy group or a glycidoxy group and may be substituted by other substituents, and R ^t is an alkyl having 1 to 10 carbon atoms which may be substituted Represents a group.
In R 2 ^s , one or more epoxy groups or glycidoxy groups may be contained, and one to three epoxy groups are preferable, and both epoxy groups and glycidoxy groups may be contained.
Specifically as the "hydrocarbon group" of the "hydrocarbon group having an epoxy group or a glycidoxy group" of R ^s , specifically, an alkyl group, a cycloalkyl group, a cycloalkylalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group And an aryl group, an arylalkyl group, an arylalkenyl group and the like can be exemplified. The number of carbon atoms is preferably in the range of 1 to 30, and more preferably in the range of 1 to 10.
As the "alkyl group", specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group, isopentyl Group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, isononyl group, n-decyl group, etc., lauryl group, tridecyl group, myristyl group, pentadecyl group, palmityl group Groups, heptadecyl groups, stearyl groups and the like can be exemplified.

Specific examples of the "cycloalkyl group" include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like.
The “cycloalkylalkyl group” is a group in which a cycloalkyl group and an alkyl group are bonded, and it is preferable that a cycloalkyl group having 3 to 10 carbon atoms and an alkyl group having 1 to 10 carbon atoms be bonded.

As the "alkenyl group", specifically, a vinyl group, prop-1-en-1-yl group, allyl group, but-1-en-1-yl group, but-2-en-1-yl group , But-3-en-1-yl group, but-1-en-2-yl group, but-3-en-2-yl group, penta-1-en-1-yl group, penta-4-ene -1-yl group, penta-1-en-2-yl group, penta-4-en-2-yl group, 3-methyl-but-1-en-1-yl group, hexa-1-ene-1 -Yl group, hexa-5-en-1-yl group, hept-1-en-1-yl group, hept-6-en-1-yl group, octa-1-en-1-yl group, octa- 7-en-1-yl group, buta-1,3-dien-1-yl group and the like can be exemplified.
As the "cycloalkenyl group", specifically, 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, 3 -A cyclohexen 1-yl group etc. can be illustrated.

  As the "alkynyl group", specifically, ethynyl group, prop-1-yn-1-yl group, prop-2-yn-1-yl group, but-1-yn-1-yl group, buta- 3-in-1-yl group, penta-1-yn-1-yl group, penta-4-yn-1-yl group, hexa-1-yn-1-yl group, hexa-5-yn-1-one Yl, hept-1-yn-1-yl, octa-1-yn-1-yl, octa-7-yn-1-yl and the like can be exemplified.

The “aryl group” means a monocyclic or polycyclic aryl group, and in the case of a polycyclic aryl group, in addition to full unsaturation, partially saturated groups are also included. Specific examples thereof include phenyl group, naphthyl group, azulenyl group, indenyl group, indanyl group, tetralinyl group and the like.
The “arylalkyl group” is a group in which an aryl group and an alkyl group are bonded, and is preferably a group in which an aryl group having 6 to 10 carbon atoms and an alkyl group having 1 to 10 carbons are bonded.
An "aryl alkenyl group" is a group which the aryl group and the alkenyl group couple | bonded, and it is preferable that it is a group which the C6-C10 aryl group and the C2-C10 alkenyl group couple | bonded.

The above-mentioned "hydrocarbon group" may be substituted by a substituent other than an epoxy group and a glycidoxy group, and as such a substituent, specifically, a halogen atom, an alkyl group, an alkenyl group, an alkoxy is mentioned. A group, a (meth) acryloxy group etc. can be illustrated.
Here, as a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. can be specifically illustrated.
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, t-butoxy group and the like.
As an alkyl group and an alkenyl group, the same specific example as the alkyl group in said R and an alkenyl group can be illustrated.

Examples of the "alkyl group having 1 to 10 carbon atoms" of the "optionally substituted alkyl group having 1 to 10 carbon atoms" of R ^t include the same as the alkyl group having 1 to 10 carbon atoms in R above. be able to.
Specific examples of the “optionally substituted” substituent include halogen atoms, alkoxy groups, (meth) acryloxy groups and the like. Specific examples of the halogen atom and the alkoxy group include the same specific examples as the halogen atom and the alkoxy group exemplified as the substituent other than the epoxy group and the glycidoxy group in the above-mentioned R.

Specifically, glycidoxyalkyl trialkoxysilane or glycidoxy alkenyl alkoxysilane is preferable as the epoxy group-containing trialkoxysilane which is a raw material or a hydrolysis condensate thereof. These can be used singly or in combination of two or more.
Specifically, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxy-n-propyltrimethoxysilane, 3-glycidoxy-n-propylmethyldiethoxysilane, 3-glycidoxypropyltrimethylsilane Mention may be made of ethoxysilanes.

2) Method of Producing Epoxy Group-Containing Trialkoxysilane Hydrolysis Condensate The epoxy group-containing trialkoxysilane hydrolysis condensate of the present invention can be produced by a conventionally known method or the like.
Specifically, a method of mixing and stirring epoxy group-containing trialkoxysilane and / or its hydrolytic condensate as a raw material, water, polyamines and, if necessary, an acid and an organic solvent can be exemplified. However, the order of mixing and the stirring speed are not particularly limited, and any order or any speed can be set. The temperature at the time of mixing and stirring is not particularly limited, and it is preferable to carry out in the range from room temperature to the boiling point of the solvent used, and it is more preferable to carry out at room temperature. In this case, the room temperature is the outside air temperature at the place where mixing and stirring are performed, but a temperature in the range of 15 to 35 ° C. is preferable.
It is preferable to stir at room temperature for 2 hours to 3 hours in the state where the epoxy group-containing trialkoxysilane, water, and all of the polyamines coexist. After hydrolysis, if necessary, dilute with an organic solvent or water.

  The amount of water to be used is not particularly limited as long as the epoxy group-containing trialkoxysilane and / or the hydrolysis condensate thereof to be used is at least an amount sufficient to hydrolytic condensation, specifically, the epoxy group-containing trialkoxy to be used 0.5 mol or more is preferable with respect to 1 mol of silanes and / or its hydrolysis condensation products, and 1.0 mol or more, 2.0 mol or more, 5.0 mol or more, or 10 mol or more is more preferable.

3) Polyamines The polyamine used in the present invention is not particularly limited as long as it is a compound having two or more amino groups or imino groups to which one or more hydrogen atoms are bonded in one molecule, and specifically Ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, methylaminopropylamine, ethylaminopropylamine, N, N'-dimethylhexamethylenediamine, Bis (2-methylaminoethyl) ether, mentan diamine, isophorone diamine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, bis (4 -Aminocyclohexyl) meta And o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-xylenediamine and the like, and these may be used singly or in combination of two or more. Can be used. Among them, polyalkylene polyamines are preferable, and specifically, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine and the like can be exemplified.
The use amount of the polyamines to be used is not particularly limited, but 1 / (on all nitrogen atoms in one polyamine molecule with respect to 1 mol of epoxy group in epoxy group-containing trialkoxysilane and / or hydrolysis condensate thereof It is preferable to use a total number of hydrogen atoms of at least 1 mole, and a range of 1.2 times to 10 times mole of 1 / (total number of hydrogen atoms on all nitrogen atoms in one polyamine molecule), 1.5 times to 5 A double molar or 1.8 to 2.5 molar range is preferable. If the amount is less than 1 / (total number of hydrogen atoms on all nitrogen atoms in one polyamine molecule), curing may be insufficient and a film having high hardness may not be obtained, 1 / (polyamines 1 When it is larger than 10 times the molar number of the total number of hydrogen atoms on the total nitrogen atoms in the molecule, polyamines may remain and a film having sufficient hardness may not be obtained.

4) Alcohol having 1 to 5 carbon atoms Alcohols used in the composition of the present invention are not particularly limited as long as they have 1 to 5 carbon atoms, and specifically, methanol, ethanol, n-propanol, Isopropanol, n-butanol, sec-butanol, tert-butanol, isobutanol, n-pentanol, isopentanol, sec-pentanol, tert-pentanol, neopentyl alcohol etc. can be exemplified, and long-term storage stability N-Pentanol is preferred in consideration of the nature.
The amount of the alcohol having 1 to 5 carbon atoms can be used in the same range as the organic solvent described later, and specifically, 3% by mass or more, preferably 4% by mass or more with respect to the entire composition. Preferably there.

5) Organic Acid The organic acid used in the composition of the present invention is an organic acid having a pKa at 25 ° C. in the range of 2.0 to 6.0, preferably in the range of 3.0 to 5.0. There is no particular limitation, and specifically, formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, caproic acid, isocaproic acid, chloroacetic acid, fluoroacetic acid, bromoacetic acid, 3-chloropropionic acid 2-bromopropionic acid, 2-hydroxybutyric acid, phenylacetic acid, phenylpropionic acid, 4-phenylbutyric acid, phenoxyacetic acid, cyanoacetic acid, oxalic acid, malonic acid, 2,2-dimethylmalonic acid, adipic acid, succinic acid, Pimelic acid, phthalic acid, glutaric acid, oxaloacetic acid, citric acid, isocitric acid, cyclohexane-1,1-dicarboxylic acid, tartaric acid, o-anisic acid, m-anisic acid, p- Anisic acid, benzoic acid, o-chlorobenzoic acid, m-fluorobenzoic acid, 2,3-difluorobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, salicylic acid, phthalic acid, ilophthalic acid, trans-cinnamic acid, 2-furancarboxylic acid, glyoxylic acid, glycolic acid, crotonic acid, lactic acid, 2-hydroxy-2-methylpropionic acid, pyruvic acid, Mandelic acid, malic acid, levulinic acid, 2,6-pyridinedicarboxylic acid, nicotinic acid and the like can be exemplified, and among them, aliphatic monocarboxylic acid, or benzoic acid or substituted benzoic acid can be preferably illustrated.
The amount of the acid used is not particularly limited, but is preferably in the range of 0.3 to 1.2 mol, 0.5 to 1.0 mol, or 0.6 to 0. 1 mol with respect to 1 mol of the polyamine used. A range of 9 moles is more preferred.
If it is less than 0.3 mol, the storage stability of the composition may be lowered, and if it is more than 1.2 mol, a coating film having sufficient hardness may not be formed.

6) Solid Content Concentration in Composition Although the solid content concentration in the composition of the present invention is not particularly limited, the appearance of the thin film, coatability, curability, properties of the thin film, storage stability of the composition, etc. are taken into consideration The range of 0.01 to 3.0 mass% is preferable, and the range of 0.05 to 2.0 mass%, 0.05 to 1.0 mass%, or 0.1 to 0.5 mass% is preferable. More preferable.
An organic solvent can be used to adjust the solid concentration in the composition. Such solvent is not particularly limited as long as it can maintain the uniformity, stability, etc. of the solution, but alcohols, ethers, ketones, esters, amides, etc. can be exemplified, and carbon The alcohol of the number 1-5 is preferable. These can be used singly or in combination of two or more.
As another solvent, it is preferable to use water, in which case the organic solvent used is preferably an organic solvent that dissolves in water. The amounts of the organic solvent and water to be used can be appropriately determined as long as the solid content concentration can be adjusted.

7) Production of Composition The method for producing the composition of the present invention is not particularly limited, and specifically, the following methods and the like can be exemplified.
i) Mix epoxy group-containing trialkoxysilane and / or its hydrolytic condensate, water and optionally an organic solvent at room temperature, then stir, add polyamines, if necessary, an organic acid, add an organic solvent, Dilute with water if necessary.
ii) Epoxy group-containing trialkoxysilane and / or its hydrolytic condensate, water, an organic solvent and polyamines are mixed and stirred at room temperature, and an organic acid is added if necessary, and further an organic solvent and if necessary Dilute with water.
iii) Epoxy group-containing trialkoxysilane and / or its hydrolytic condensate, water, alcohol as solvent, polyamines, and optionally organic acid are mixed and stirred at room temperature, and organic solvent and, if necessary, water Dilute with
iv) The epoxy group-containing trialkoxysilane, water, an alcohol as a solvent, a polyamine and optionally an organic acid are mixed and stirred at room temperature.
The stirring temperature is not particularly limited, but is preferably in the range of room temperature to the boiling point of the solvent used, more preferably at room temperature. In this case, the room temperature is the outside temperature of the place where the stirring is performed, but a range of 15 to 35 ° C. is preferable.

8) Method of Surface Treatment The above-mentioned composition for thin film formation of the present invention can form a thin film on the surface of a fishhook which is a target object by any known application means such as brush, spray, dipping and the like. Drying can be performed by room temperature drying and / or heating. Specifically, it is performed at 20 ° C. to 250 ° C., preferably 20 ° C. to 150 ° C., for 10 seconds to 24 hours, preferably about 30 seconds to 10 hours.
The thin film to be obtained is not particularly limited, but is preferably more than 10 nm and 5 μm or less.
After forming the thin film, it is preferable to introduce a hydrophilic group on the thin film surface by partially oxidizing the thin film surface in the above-described plasma atmosphere containing oxygen, corona treatment, or the like.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but the technical scope of the present invention is not limited thereto.

Example 1
In a glass container, put 100 needles (XP Air Speed, size: 6.5, manufactured by DAIWA) in advance, 4 times in advance with toluene, 2 times with acetone, 1 time with pure water, isopropanol (hereinafter referred to as IPA) There was one ultrasonic cleaning for 10 minutes each at a time.
After the ultrasonic cleaning was completed, the needle was dried at 60 ° C. for 30 minutes, and immersed in a 1 M aqueous solution of sodium metasilicate at normal temperature for 30 minutes.
After the treatment with an aqueous solution of sodium metasilicate, the solution was thoroughly washed with pure water to remove the aqueous solution of sodium metasilicate, and further washed with IPA and dried at 60 ° C. for 30 minutes.
Next, the substrate is immersed in a surface treatment composition (SAMLAY (registered trademark), Nippon Soda Co., Ltd.) for 30 minutes, washed with n-decane, and dried at 60 ° C. for 30 minutes to form an organic thin film I got one.

Example 2
In a glass container, 100 nickel plated needles (XP Air Speed, size: 6.5, manufactured by DAIWA) are placed, 4 times in advance with toluene, 2 times with acetone, 1 time with pure water, 1 time with IPA Ultrasonic cleaning for 10 minutes each time.
After the ultrasonic cleaning was completed, the needle was dried at 60 ° C. for 30 minutes, and immersed in a 1 M aqueous solution of sodium metasilicate at normal temperature for 30 minutes.
After the treatment with an aqueous solution of sodium metasilicate, the solution was thoroughly washed with pure water to remove the aqueous solution of sodium metasilicate, and further washed with IPA and dried at 60 ° C. for 30 minutes.
Next, the substrate is immersed in a surface treatment composition (SAMLAY (registered trademark), Nippon Soda Co., Ltd.) for 30 minutes, washed with n-decane, and dried at 60 ° C. for 30 minutes to form an organic thin film I got two.

[Example 3]
In a glass container, put 100 nickel-plated needles (XP air speed, size: 6.5), and ultrasonically clean once with toluene four times, twice with acetone, once with pure water, and once with IPA. Was done for 10 minutes each time.
After the ultrasonic cleaning was completed, the needle was dried at 60 ° C. for 30 minutes, and immersed in a 1 M aqueous solution of sodium metasilicate at normal temperature for 30 minutes.
After the treatment with an aqueous solution of sodium metasilicate, the solution was thoroughly washed with pure water to remove the aqueous solution of sodium metasilicate, and further washed with IPA and dried at 60 ° C. for 30 minutes.
Next, after immersing for 30 minutes in the composition for surface treatments prepared by the method of the patent 4995467 using nona fluoro hexyl trimethoxysilane, it wash | cleans by HFE-7300 (made by Sumitomo 3M), The film was dried at 30 ° C. for 30 minutes to obtain a needle 3 having a fluorine-based organic thin film formed thereon.

Example 4
In a glass container, 100 nickel plated needles (XP Air Speed, size: 6.5, manufactured by DAIWA) are placed, 4 times in advance with toluene, 2 times with acetone, 1 time with pure water, 1 time with IPA Ultrasonic cleaning for 10 minutes each time.
After the ultrasonic cleaning was completed, the needle was dried at 60 ° C. for 30 minutes, and immersed in a 1 M aqueous solution of sodium metasilicate at normal temperature for 30 minutes.
After the treatment with an aqueous solution of sodium metasilicate, the solution was thoroughly washed with pure water to remove the aqueous solution of sodium metasilicate, and further washed with IPA and dried at 60 ° C. for 30 minutes.
Next, the substrate is immersed in a fluorine-based surface treatment agent (Novec (registered trademark) EGC-1720 (manufactured by Sumitomo 3M) for 30 minutes and then dried at 60 ° C. for 30 minutes to obtain a needle 4 on which a fluorine-based organic thin film is formed. The

[Example 5]
In a glass container, 100 gold plated spatula needles were placed, and ultrasonic cleaning was performed once for 10 minutes each for IPA four times with toluene, twice with acetone, once with pure water, and once with IPA. .
After completion of the ultrasonic cleaning, the spatula needle was dried at 60 ° C. for 30 minutes, and immersed in a 30% hydrogen peroxide solution for 30 minutes at room temperature.
After treatment with a 30% hydrogen peroxide solution, the resultant was thoroughly washed with pure water, further washed with IPA, and dried at 60 ° C. for 30 minutes.
Next, it was immersed in a toluene solution of 0.5% octadecanethiol for 30 minutes, then washed with toluene, and dried at 60 ° C. for 30 minutes to obtain a spatula needle 1 having a thiol-based organic thin film formed.

[Test Example 1] Evaluation by piercing test (1)
The needle on which the organic thin film was formed was measured and evaluated for piercing stress and penetration stress by a piercing test on a film or various materials. In FIG. 1, the test result about the needle 1 obtained in Example 1 is shown. As a testing machine, a precision universal testing machine (manufactured by Shimadzu Corporation) was used.
The piercing test to Cellotape (registered trademark) (tape width 18 mm, manufactured by Nichiban Co., Ltd.) was performed as a material using the needles 1 to 4 on which the organic thin films of Examples 1 to 5 were formed and the spatula needle 1. Table 1 and Table 2 show the stresses of penetration and penetration, respectively. The reduction rate was determined by comparing with each untreated fishhook.

[Test Example 2] Evaluation by piercing test (2)
The test was conducted in the same manner as in Test Example 1 except that Japanese paper (width 20 mm, manufactured by Dainippon Co., Ltd.) was used as a material.

[Example 6]
4.95 g of diethylenetriamine and 693.07 g of water were added to and mixed with a solution obtained by dissolving 4.95 g of benzoic acid in 277.23 g of IPA. Further, 19.80 g of 3-glycidoxypropyltrimethoxysilane was added to this solution and reacted at room temperature for 2 hours to prepare a composition [A-1] of 3% in terms of mass concentration of solid content.
A composition for forming a thin film having a concentration by mass conversion of solid content of 0.3% was obtained by diluting 5.0 g of the obtained composition [A-1] with a solvent prepared by mixing 12.86 g of propylene glycol monomethyl ether and 32.14 g of water. An object [X-1] was obtained.

The surface of a clear-coated acupuncture needle (Hagashi S), which has been washed in order of pure water and IPA in advance, is dip-coated with the thin film-forming composition [X-1], and then dried by heating at 100 ° C. for 10 minutes. The fishhook [Y-1] was produced. Subsequently, the obtained hook [Y-1] was treated by UV ozone washing (about 12000 mJ / cm ² ) for 10 minutes.

  The above-mentioned UV ozone-cleaned fishing hook [Y-1] was immersed in a surface treatment composition (SAMLAY (registered trademark), Nippon Soda Co., Ltd.) for 10 minutes. Thereafter, the surface of the hook was rinsed with a hydrocarbon detergent (NS Clean 100, manufactured by JX Nippon Oil & Energy) and dried at 60 ° C. for 20 minutes to obtain a hook according to the present invention.

[Example 7]
After dip coating the surface of the clear needle coated on a gold plating that has been washed in advance with pure water and IPA in the order of gold plating with the composition for forming a thin film [X-1], it is dried by heating at 100 ° C. for 10 minutes. [Y-1] was produced. Subsequently, the obtained hook [Y-1] was treated by UV ozone washing (about 12000 mJ / cm ² ) for 10 minutes.

  The above-mentioned UV ozone-cleaned fishing hook [Y-1] was immersed in a surface treatment composition (SAMLAY (registered trademark), Nippon Soda Co., Ltd.) for 10 minutes. Thereafter, the surface of the hook was rinsed with a hydrocarbon detergent (NS Clean 100, manufactured by JX Nippon Oil & Energy) and dried at 60 ° C. for 20 minutes to obtain a hook according to the present invention.

[Example 8]
After dip-coating the surface of a red-painted nut needle that has been washed in order of pure water and IPA in advance with the composition for forming a thin film [X-1], it is heated and dried at 100 ° C. for 10 minutes to obtain a fishhook [Y- 1] was produced. Subsequently, the obtained hook [Y-1] was treated by UV ozone washing (about 12000 mJ / cm ² ) for 10 minutes.

  The above-mentioned UV ozone-cleaned fishing hook [Y-1] was immersed in a surface treatment composition (SAMLAY (registered trademark), Nippon Soda Co., Ltd.) for 10 minutes. Thereafter, the surface of the hook was rinsed with a hydrocarbon detergent (NS Clean 100, manufactured by JX Nippon Oil & Energy) and dried at 60 ° C. for 20 minutes to obtain a hook according to the present invention.

[Example 9]
After dip-coating the surface of the triple hook which has been clear-coated on the tin plating that has been washed in advance with pure water and IPA in this order with the composition for forming a thin film [X-1], it is dried by heating at 100 ° C. for 10 minutes. [Y-1] was produced. Subsequently, the obtained hook [Y-1] was treated by UV ozone washing (about 12000 mJ / cm ² ) for 10 minutes.

  The above-mentioned UV ozone-cleaned fishing hook [Y-1] was immersed in a surface treatment composition (SAMLAY (registered trademark), Nippon Soda Co., Ltd.) for 10 minutes. Thereafter, the surface of the hook was rinsed with a hydrocarbon detergent (NS Clean 100, manufactured by JX Nippon Oil & Energy) and dried at 60 ° C. for 20 minutes to obtain a hook according to the present invention.

[Test Example 3] Evaluation by piercing test (3)
The needle with the organic thin film of Example 6 was subjected to a piercing test with Sellotape (registered trademark) (tape width 18 mm, manufactured by Nichiban Co., Ltd.) as a material. Table 4 and Table 5 show the stresses of penetration and penetration, respectively. The reduction rate was determined by comparison with an untreated hook.

[Test Example 4] Evaluation by piercing test (4)
The needle | hook which formed the organic thin film of Examples 7-9 performed the piercing test to a silicon sheet (1.0 mm thickness) as a material. Table 4 and Table 5 show the stresses of penetration and penetration, respectively. The reduction rate was determined by comparing with each untreated fishhook.

  From the above results, it was found that by forming an organic thin film, in particular, a needle with reduced penetration stress can be produced.

Claims (3)

Formula (I)
R ¹ _n MX _m-n (I)
(Wherein, R ¹ represents a hydrocarbon group having 1 to 30 carbon atoms or a halogenated hydrocarbon group having 1 to 30 carbon atoms, M represents a silicon atom, and X represents a hydroxyl group or a hydrolysable group. And m represents a valence of M. n represents a positive integer of 1 to (m-1), and when n is 2 or more, R ¹ may be the same or different. When (m−n) is 2 or more, X may be the same or different, and at least one is a hydroxyl group or a hydrolysable group), at least one or more hydroxyl groups or Metallic surfactants having hydrolyzable groups,
From fluorochemical surface treatment agents other than metal surfactants having a fluoroalkyl or poly (fluoroalkyleneoxy) and having a functional group at the end and having at least one or more hydroxyl groups or hydrolysable groups , thiol compounds and disulfide compounds A fishing hook surface-treated with a compound selected from the group consisting of The fishing hook according to claim 1, wherein the fishing hook has been previously washed with an alkaline aqueous solution. In advance, the hook
(A) Hydrolysis condensation product of epoxy group-containing trialkoxysilane,
(B) an alcohol having 1 to 5 carbon atoms, and / or an organic acid having a pKa at 25 ° C. in the range of 2.0 to 6.0, and
(C) A fishing hook according to claim 1 , which is a fishing hook surface-treated with a thin film-forming composition containing polyamines.